Linear homobimetallic palladium complexes

Lang, Heinrich; Taher, Deeb; Walfort, Bernhard; Pritzkow, Hans

doi:10.1016/j.jorganchem.2006.05.034

Cited by 15 publications

(6 citation statements)

References 94 publications

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“…Conjugated one-dimensional rods have been the centre of attention of several recent studies related to the development of molecular electronic devices such as wires, switches or insulators. [1][2][3][4][5][6][7] It is well known that the incorporation of transition metal centers enables even finer tuning of the properties of these rods. [8][9][10][11] Transition metal alkynyl complexes, with their ability to perturb electronic properties through metal alkynyl dπ-pπ interactions, 12,13 are primary candidates for the preparation of metallomolecular devices.…”

Section: Introductionmentioning

confidence: 99%

“…28 If Pd-σ-alkynyls are often used for the preparation of homometallic 3,4,[29][30][31][32][33] or heterometallic [34][35][36] (with the incorporation of Ru, Fe or Ni metal centers) organometallic polymers, the synthesis of discrete binuclear Pd rods is comparatively much more scarce and is not so often found in the literature. 5,[37][38][39] Previous studies showed that [PdCl 2 (PEt 3 ) 2 ] compounds form square planar systems with the bridging oligophenylene ligands. 15 Consequently, an increase of the π delocalization from the ring to the metal center would be expected, which could improve the conducting properties of the rod.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis, characterization and solid-state photoluminescence studies of six alkoxy phenylene ethynylene dinuclear palladium(ii) rods

et al. 2015

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A rare family of six discrete binuclear [PdCl(PEt3)2] phenylene ethynylene rods with alkoxy side chains (methoxy, ethoxy and heptoxy) have been developed, and their solid-state photoluminescence results have been presented and discussed. The shorter bridging ligands are of the general formula H-C≡C-C6H2(R)2-C≡C-H, where R = H, OCH3, OC2H5, and OC7H15, whereas the longer ones are based on H-C≡C-C6H4-C≡C-C6H2(R)2-C≡C-C6H4-C≡C-H, where R = OCH3, OC2H5. These ligands display increasing length in both the main dimension (backbone length) as well as the number of carbons in the side chains (R, alkoxide side chain) that stem from the central phenylene moiety. The X-ray crystal structures of two of the prepared complexes are reported: one corresponds to a shorter rod, 1,4-bis[trans-(PEt3)2ClPd-C≡C]-2,5-diethoxybenzene (6c), while the second one is associated with a longer rod, the binuclear complex 1,4-bis[trans-(PEt3)2ClPd-4-(-C≡C-C6H4-C≡C)]-2,5-diethoxybenzene (7c). All new compounds were characterized by NMR spectroscopy ((1)H, (13)C{(1)H} and (31)P{(1)H}) as well as ESI-MS(TOF), EA, FTIR, UV-Vis, cyclic voltammetry and solid-state photoluminescence. Our work shows the influence of the alkoxy side chains on the electronic structure of the family of binuclear Pd rods by lowering its oxidation potential. In addition to this, the increase of the length of the bridge results in a higher oxidation potential. Solid state photoluminescence results indicate that Pd complexes are characterized by a marked decrease in both the emission intensity and the fluorescence lifetime values as compared to their ligands. This behaviour could be due to some degree of ligand-to-metal charge transfer.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and solid-state photoluminescence studies of six alkoxy phenylene ethynylene dinuclear palladium(ii) rods

et al. 2015

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“…Cationic palladium complexes are known and can be readily prepared in a form close to [L 2 Pd(Ar)] + by stabilizing the complex with a weakly bound donor ligand. 64 Accordingly, an untagged palladium cation complex was independently synthesized and isolated as the 4-methylpyridine adduct (Figure 14).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Real-Time Mass Spectrometric Investigations into the Mechanism of the Suzuki–Miyaura Reaction

et al. 2018

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Real-time monitoring of the Suzuki–Miyaura reaction using mass spectrometry during sequential addition of the various reaction components suggests that a dynamic series of equilibria exist in these solutions. Depending on conditions, the boronic acid can be dehydrated, deprotonated, hydroxylated (or alkoxylated), or fluorinated. Palladium–phosphine species present include Pd(0) (to which the aryl iodide rapidly oxidatively adds), the Pd(II) aryl iodide complex, a cationic Pd(II) species formed by dissociation of the iodide ligand, and the Pd(II) bisaryl complex that ultimately extrudes the product through reductive elimination. No fluorinated or hydr(alk-)oxylated palladium complexes were observed under catalytic conditions. Several transmetalation combinations were excluded as reactive partners, but several possibilities remain, and more than one mechanism is likely to be operative, even under similar conditions.

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“…For related palladium(II) complexes with 4-cyanopyridine, see: Kopylovich et al (2009); Lang et al (2006); Taher et al (2006).…”

Section: Related Literaturementioning

confidence: 99%

Tetrakis(4-cyanopyridine)palladium(II) bis(trifluoromethanesulfonate)

et al. 2010

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The title salt, [Pd(C6H4N2)4](CF3SO3)2, comprises Pd(4-cyanopyridine)4 dications balanced by two trifluoromethanesulfonate anions. The PdII atom lies in a square-planar geometry defined by four N atoms which form equivalent Pd—N interactions. The 4-cyanopyridine ligands are twisted out of the N4 plane, forming dihedral angles ranging from 66.5 (2) to 89.9 (2)°. In the crystal packing, columns of edge-to-edge dications define channels in which reside the anions. A range of C—H⋯N and C—H⋯O hydrogen-bonding interactions stabilizes the crystal packing.

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Linear homobimetallic palladium complexes

Cited by 15 publications

References 94 publications

Synthesis, characterization and solid-state photoluminescence studies of six alkoxy phenylene ethynylene dinuclear palladium(ii) rods

Synthesis, characterization and solid-state photoluminescence studies of six alkoxy phenylene ethynylene dinuclear palladium(ii) rods

Real-Time Mass Spectrometric Investigations into the Mechanism of the Suzuki–Miyaura Reaction

Tetrakis(4-cyanopyridine)palladium(II) bis(trifluoromethanesulfonate)

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